Adducts of heterocyclic amides



United StatesPatent G 3,021,338 ADDUCTS F HETEROCYCLIC AMIDES Newman M. Bortnick, Oreland, Pa., assignor to Rohm dz Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Filed Dec. 5, 1956, Ser. No. 626,294 5 Claims. (Cl. 260--309.7)

in which L is a threeto four-membered divalent chain containing two to three carbon atoms and one nitrogen atom, and Y is a chalcogen having an atomic weight of 16 to 32, i.e., oxygen or sulfur. There must be at least two carbon atoms between the nitrogen atoms of the heterocyclic amide considered in a counterclockwise direction. The carbon atoms may have their remaining valences satisfied by hydrogen atoms, by alkyl groups whose total carbon atom content is no greater than eighteen, or by combinations of hydrogen atoms and alkyl groups. When L contains two carbon atoms there are four valences to be satisfied by hydrogen atoms, alkyl groups, or combinations thereof. For instance, there may be four hydrogen atoms, four alkyl groups, three hydrogen atoms and one alkyl group, two hydrogen atoms and two alkyl groups, or one hydrogen atom and three alkyl groups. When L contains three carbon atoms there are six valences to be satisfied by hydrogen atoms, alkyl groups, or combinations thereof and these valences may be satisfied in a way analogous to the manner described above when L contained two carbon atoms. It is also possible for the above-mentioned alkyl substituents to be joined together to form carbocyclic rings in conjunction with the L chain.

The nitrogen atom in the L chain must occupy a position at least two carbon atoms removed from the other nitrogen atom in the heterocyclic amide. It is preferred that it be vicinal to the carbonyl carbon when L contains either three or four members, or when L contains four members the nitrogen atom in L may be one carbon atom removed from the carbonyl carbon. Also, when the nitrogen atom of L is vicinal to the carbonyl carbon atom and L contains three carbon atoms the middle carbon atom of L may contain a hydroxy substituent.

The nitrogen atom in the L chain may have its remaining valence satisfied by a hydrogen atom, an alkyl, including cycloalkyl and alkylcycloalkyl groups of one to eighteen carbon atoms, an aryl, alkylaryl, arylalkyl, or alkylarylalkyl group of six to eighteen carbon atoms, a hydroxyalkyl group of two to eight carbon atoms in which the hydroxy group is no closer than the beta position with respect to the nitrogen atom concerned, an alkenyl group of two to eighteen carbon atoms, an aminoalkyl group of two to eight carbon atoms in which the amino group is no closer than the beta position with respect to the ring nitrogen atom, an alkoxyalkyl group containing up to nineteen carbon atoms in which the alkoxy portion contains up to eight carbon atoms and the alkyl portion contains at least two carbon atoms, an alkenoxyalkyl group of up to nineteen carbon atoms in which the alkenoxy portion contains up to eight carbon atoms and the alkyl portion contains at least two carbon atoms, a cyano group, and a cyanoalkyl group in which the alkyl part contains up to eight carbon atoms.

The alkyl substituents on the carbon atoms of the L chain may have any possible spatial configuration, such as normal, iso-, tertiary, and the like. Likewise, the alkyl and alkenyl substituents and substituted groups thereof on the nitrogen atom in the L chain may have any possible spatial structure. Also, alkyl groups on saturated or unsaturated cyclic substituents may occupy any possible spatial, position. The double bond in the alkenyl groups may be at any possible location.

Typical of the alkyl substituents that may be used to satisfy the remaining valences of the carbon atoms in the L chain include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, tridecyl, and octadecyl groups.

Typical of the substituents, other than a hydrogen atom, that may satisfy the remaining valence of the nitrogen in the L chain include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, .cyclobutyl, cyclopentyl, propylcyclopentyl, octylcyclopentyl, cyclohexyl, butylcyclohexyl, vinyl, al-

lyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, de-

cenyl, dodecenyl, octadecenyl, phenyl, benzyl, phenylethyi, phenylbutyl, phenyloctyl, phenyldodecyl, butylphenylpentyl, butylphenyl, octylphenyl, dodecylphenyl, naphthyl, naphthylethyl, naphthylbutyl, napthyloctyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyoctyl, aminoethyl, aminopropyl, aminobutyl, aminopentyl, aminooctyl, methoxyethyl, methoxybutyl, methoxyheptyl, methoxydecyl, methoxytetradecyl, methoxyoctadecyl, ethoxyethyl, ethoxybutyl, ethoxyhexyl, ethoxydecyl, ethoxydodecyl, propoxyethyl, propoxypropyl, propoxypentyl, propoxyoctyl, propoxyhexadecyl, butoxyethyl, butoxypropyl, butoxybutyl, butoxyhexyl, butoxyoctyl, butoxydecyl, butoxydodecyl, butoxytetradecyl, pentoxyethyl, pentoxypropyl, pentoxybutyl, pentoxydecyl, pentoxydodecyl, pentoxytetradecyl, hexoxyethyl, hexoxypropyl, hexoxybutyl, hexoxyhexyl, hexoxydecyl, hexoxydodecyl, heptoxyethyl, heptoxypropyl, heptoxybutyl, heptoxyheptyl, heptoxyoctyl, heptoxydodecyl, octoxyethyl, octoxypentyl, octoxyoctyl, octoxynonyl, octoxydecyl, nonoxyethyl, nonoxypentyl, nonoxynonyl, nonoxydecyl, decoxyethyl, decoxypentyl, decoxyheptyl, decoxynonyl, undecoxyethyl, undecoxyhexyl, dodecoxyethyl, dodecoxyhexyl, tridecoxyethyl, tridecoxyhexyl, tetradecoxyethyl, tetradecoxypentyl, pentadecoxyethyl, pentadecoxybutyl, hexadecoxyethyl, hexadecoxypropyl, vinoxyethyl, vinoxypropyl, vinoxybutyl, vinoxypentyl, vinoxyhexyl, vinoxyoctyl, vinoxynonyl, vinoxydecyl, vinoxydodecyl, vinoxytetradecyl, vinoxyhexadecyl, alloxyethyl, alloxypentyl, alloxyoctyl, alloxyundecyl, alloxytetradecyl, alloxyhexadecyl, butenoxyethyl, butenoxybutyl, butenoxyheptyl, butenox'ydecyl, butenoxydodecyl, butenoxypentadecyl, pentenoxyethyl, pentenoxypentyl, pentenoxydecyl, pentenoxytetradecyl, hexenoxyethyl, hexenoxyhexyl, hexenoxynonyl, hexenoxytridecyl, heptenoxyethyl, heptenoxypentyl, heptenoxyheptyl, heptenoxydodecyl, octenoxyethyl, octenoxybutyl, octenoxyhexyl, octenoxyoctyl, octenoxydecyl, nonenoxyethyl, nonenoxypentyl, nonenoxynonyl, nonenoxydecyl, decenoxyethyl, decenoxypropyl; decenoxybutyl, decenoxyhexyl, decenoxynonyl, undecenoxyethyl, undecenoxybutyl, undecenoxyoctyl, dodecenoxyethyl, dodecenoxybutyl, dodecenoxyheptyl, tridecenoxyethyl, tridecenoxyhexyl, tetradecenoxyethyl, tetradecenoxypentyl, pentadecenoxyethyl, pentadecenoxybutyl, hexadecenoxyethyl, heptadecenoxyethyl, cyano, cyanomethyl, cyanoethyl, cyanopropyl, cyanobutyl, cyanopentyl, cyanoheptyl, cya-, nooctyl groups, and the like.

It is preferred that both of the nitrogen atoms in the l-cyano-4,4-dimethyl-2piperimidinone, l- (Z-cyanobutyl) -4octadecyl-2-piperimidinthione.

The mil-unsaturated compounds employed in this invention correspond to the formula in which Q is a hydrogen atom, an alkyl group of one to eight carbon atoms, or the group to be more fully described hereinafter. T may stand for a cyano group, the group -CONZ in which Z may stand for a hydrogen atom or an alkyl group of one to four carbon atoms, or the group -COOR. The symbol R represents a monovalent esterifying group of preferably one to fourteen carbon atoms and, preferably, alkyl groups of one to fourteen carbon atoms, alkoxyalkyl groups of two to fourteen carbon atoms, aralltyl and alkaralkyl groups of seven to fourteen carbon atoms, and cycloalkyl and 'alkylcycloalkyl groups of three to fourteen carbon atoms. The alkyl groups may be straight or branched chains in any of the known spatial configurations. The alkyl groups positioned on cyclic structures may occupy any possible ring location.

Typical of the representations of Q include a hydrogen atom, the groups methyl, ethyl, propyl, butyl, hexyl, and octyl, and the groups CH CH CH(CH )T.

Typical of the groups that may be employed as T include cyano, carbamoyl, methylcarbamoyl, ethylcarbamoyl, propylcarbamoyl, butylcarbamoyi, dimethylcar bamoyl, diethylcarbamoyl, dibutylcarbamoyl, methylethylcarbamoyl, ethylbutylcarbamoyl, propylbutylcarbamoyl, methoxycarbonyl, ethoxycarbonyl, propoxy carbonyl, butoxycarbonyl, octoxycarbonyl, dodecoxycarbonyl, tetradecoxyc-arbonyl, methoxymethoxycarbonyl, methoxyethoxycarbonyl, methoxypropoxycarbonyl, methoxybutoxycarbonyl, methoxyoctoxycarbonyl, methoxydecoxycarbonyl, ethoxymethoxycarbonyl, ethoxyethoxycarbonyl, ethoxypropoxycarbonyl, ethoxyoctoxycarbonyl, propoxyethoxycarbonyl, propoxypropoxycarbonyl, propoxypentoxycarbonyl, propoxyheptoxycarbonyl, butoxymethoxycarbonyl, butoxyethoxycarbonyl, butoxybutoxycarbonyl, butoxynonoxycarbonyl, butoxydecoxycarbonyl, pentoxymethoxycarbonyl, pentoxybutoxycarbonyl, pentoxypentoxycarbonyl, pentoxyhexoxycarbonyl, pentoxyoctoxycarbonyl, hexoxyrnethoxycarbonyl hexoxypropoxycarbonyl, hexoxyhexoxycarbonyl, hexoxyoctoxycarbonyl, heptoxymethoxycarbonyl, heptoxybutoxycarbonyl, heptoxyheptoxycarbonyl, octoxymethoxycarbonyl, octoxyethoxycarbonyl, octoxybutoxycarbonyl, octoxyhexoxycarbonyl, benzoxycarbonyl, phenylethoxycarbonyl, phenylbutoxyoarbonyl, ethylbenzoxycarbonyl, phenylbutoxycarbonyl, phenylhexoxycarbonyl, phenyloctoxycarbonyl, butylbenzoxycarbonyl, naphthylmethoxycarbonyl, naphthylethoxycarbonyl, naphthylpropoxycarbonyl, naphthylbutoxycarbonyl, cyclopropoxycar-bonyl, cyclobutoxycarbonyl, cyclopentoxycarbonyl, cyclohexoxycarbonyl, butylcyclopentoxycarbonyl, octylcyclohexoxycarbonyl, cyclopentylheptoxycarbonyl, and cyclohexyloctoxycarbonyl.

Illustrative of the a,,8-unsaturated compounds that may be used as reactants in this invention include acrylonitrile, methacrylonitrile, a-butylacrylonitrile, qt-OC'CYlHCi'YlOIlltrile, acrylamide, methacrylamide, wethylacrylamide, propylacrylamide, u-octylacrylamide, N-methylacrylamide,, N,N-dimethylacrylamide, N-ethylmethacrylamide, N-ethyl-N-propylmethacrylamide, N-methyl-a-ethylacrylamide, N-methyl-N-butyl-a-propylacrylamide, N,N-di(2- ethylhexyl)acrylamide, N,N-dimethyl-u-octylacrylamide, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, dodecyl acrylate, tetradecyl acrylate, methyl methacrylate, butyl methacrylate, decyl methacrylate, methyl ethacrylate, ethyl ethacrylate, octyl ethacrylate, methyl a-propylacrylate, butyl a-propylacrylate, nonyl a-propylacrylate, methyl a-butylacrylate, propyl a-butylacrylate, heptyl a-butylacrylate, methyl a-hexylacrylate, pentyl a-hexylacrylate, undecyl a-hexylacryl-ate, butyl aheptylacrylate, methyl et-octylacrylate, dodecyl u-octylacrylate, methoxyethyl acrylate, methoxydecyl acrylate, ethoxypropyl acrylate, butoxyhexyl acrylate, methoxymethyl methacrylate, propoxydecyl methacrylate, ethoxyethyl ethacrylate, butoxyoctyl ethacrylate, methoxydodecyl a-propylacrylate, pentoxypentyl a-propylacrylate, methoxybutyl a-butylacrylate, butoXyheXyl a-butylacrylate, ethoxyheptyl u-pentylacrylate, methoxyoctyl a-hexylacrylate, propoxybutyl a-heptylacrylate, butoxybutyl w octylacrylate, benzyl acrylate, naphthylmethyl acrylate, phenylethyl methacrylate, naphthylethyl methacrylate, benzyl ethacrylate, naphthylbutyl ethacrylate, phenyloctyl a-propylacrylate, naphdlylethyl a-butylacrylate, octylphenylethyl ot-pentylacrylate, benzyl a-hexylacrylate, naphthylmethyl a-heptylacrylate, phenylhexyl a-OCtYlacrylate, cyclohexyl acrylate, cyclopentyl methacrylate, cyclohexyl ethacrylate, cyclobutyl u-octylacrylate, dimethyl a-methylene-a'-methyladipate, methyl hexyl amethylene-u'-methyladipate, dimethoxyethyl d-mthyll1- uU-methyladipate, hexoxyethyl methyl a-methylene-odmethyladipate, methyl benzyl u-methylene-ot'-methyl adipate, dibenzyl a-methylene-ot-methyladipate, methyl cyclohexyl ot-methylene-a'-methyladipate, dicyclopentyl a-methylene-u'-methyladipate, methyl octylcyclohexyl ozmethylene-a'-methyladipate, ethyl naphthylethyl a-met ylene a methyladipate, tat-methylene-u-methyladiponitrile, tat-methylene-u'-methyladipamide, N, N'-dirnethylwmethylene-a-methyladipamide, N,N'-dibutyl-ot-methylene-a'-methyladipamide, N-butyl-N'-methyl-a-metl1ylene adipamide, N,N,N',N-tetramethyl-a-methylene-a-methyladiparnide, 2-methylene-5-cyanohexanamide, N-methyI-Z-methylene-5-cyanohexanamide, N-methyl-N-butyl-Z- methylene-5-cyanohexanamide, N,N-diethyl-2-methylene- S-cyanohexanamide, Z-methyl-S-cyano-5-hexenamide, N- methyl-2-methyl-5-cyano-S-hexenamide, N,N-dimethyl-2- methyl-S-cyano-S-hexenamide, N-methyl-N-butyl-Z-methyl-S-cyano-S-hexenamide, methyl Z-methyl-S-cyano-S- hexenoate, dodecyl 2-methyl-5-cyano-5-hexenoate, butoxyethyl 2-methyl-5-cyano-5-hexenoate, pentoxypentyl Z-methyl-S-cyano-S-hexenoate, benzyl Z-methyl-S-cyano- S-hexenoate, naphthylethyl 2-methyl-S-cyano-S-hexenoate, cyclohexyl Z-methyl-S-cyano-5-hexenoate, methyl 2- methylene-S-cyanohexanoate, octyl Z-methylene-S-cyanohexanoate, methoxyethyl 2-methylene-5-cyanohexanoate, butoxybutyl 2-rnethylene-S-cyanohexanoate, octylphenylethyl Z-methylene-S-cyanohexanoate, naphthylbutyl 2- methylene-5-cyanohexanoate, cyclopentyl Z-methylene-S- cyanohexanoate, methyl Z-methyl-S-carbamoyl-S-hexeno ate, ethyl Z-methyl-S-methylcarbamoyl-5-hexeuoate, decyl 2-methyl-5-dimethylcarbamoyl-S-hexenoate, ethoA ethyl Z-methyl-S-methylpropylcarbamoyl-S-hexenoate, octoxybutyl 2-methyl-5-butylcarbamoyl-S-hextnoate, benzyl Z-methyl-S-ethylcarbamoyl-S-hexenoate, cyclohexyl 2- methyl-S-carbamoy1-5-hexenoate, butyl Z-methylene-S- carbamoylhexanoate, tetradecyl Z-methylene-S-carbamoylhexanoate, methoxyhexyl Z-methylene-S-methylcarbamoylhexanoate, butoxypropyl 2-rnethylene-S-diethylcarbamoylhexanoate, benzyl 2-rnethylene-5-methylethylcarbamoylhexanoate, naphthylpropyl 2-methylene-5-propylcarbamoylhexanoate, and cyclopentyl Z-methylene-S- dipropylcarbamoylhexanoate.

The reactants of this invention are compounds that are known or can be made by known methods. Two principal types of stable products are possible from the present process. When each of the nitrogen atoms in the heterocyclic amide reactant bears a hydrogen atorn' the predominant product is the one in which two equivalents of the defined afi-unsaturated reactant unites with one equivalent of the hetero-cyclic amide. When the nitrogen atom in the L chain of the heterocyclic amide bears a substituent group, that is, when it has no hydrogen atom connected directly to it, the product formed is the adduct of substantially equimolecular amounts of the dc 7 fined heterocyclic amide and the mil-unsaturated compound reactants. While the 2:1 adduct is preferred, either type of product is satisfactory for the present purposes. a

It is also possible, in some instmces, when the nitrogen atom in the L chain of the heterocyclic amide contains a hydroxyalkyl substituent and the a,/3-unsaturated compound contains at least one ester group, to obtain a prod not in which one equivalent of the a d-unsaturated compound adds to the nitrogen atom of the heterocyclic amide not in the 'L chain, and another equivalent adds to the hydroxyalkyl substituent by transesterification. These products are quite satisfactory for the present purposes.

The products or this invention are made by bringing together at a reacting temperature in the presence of a strong alkaline catalyst a compound having the formula with one having the formula CHz=C|l-T Q in which the symbols have the significance previously set forth. Temperatures in the range of about to 200 C. are advantageously employed, with a range of about 25 to'175 C. preferred.

The 0:,fi-UI1S3lZUIfl'EGd compounds are all liquids and the heterocyclic amides are generally solids. Since at least one of the reactants is always a liquid a solvent is not absolutely necessary. However, in many instances, it is advantageous to employ an inert volatile organic solvent such as methanol, ethanol, butanol, benzene, toluene,

, xylene, dioxane, diethyl ether, dimethyl ether of ethylene glycol, and the like. At the conclusion of the reaction the solvent is readily removed such as by stripping, preferably at reduced pressures.

The present reaction is exothermic in nature and it is frequently advantageous to conduct the reaction by first adding all of the predetermined equivalent amount of the selected heterocyclic' amide reactant to a reaction vessel along with the catalyst and a portion of the predetermined equivalent amount of the zip-unsaturated compound reactant. In some cases, the above mixture requires some heating in order to initiate the reaction, after which a considerable heat of reaction becomes apparent. As the heat of reaction abates, additional portions of the ct, 3-unsaturated compound are introduced into the reaction vessel until all of the predetermined amount has been used; By using the, above-described procedure, the present reaction is consistently conducted in an orderly manner. In many instances, it is entirely satisfactory to introduce all of the predetermined amounts or" both of the reactants, particularly when the reactants have the higher molecular weights or substituent groups occupying considerable molecular space or both, in which situations a retarding ponderal effect is readily observable.

The time of reaction is not critical. Generally, times of about one-half hour to twenty-four hours are used, as conditions indicate. it is usually advantageous to conduct the present method for about an hour or two after the heat of reaction is finally dissipated. This is to maximize yields. Otherwise, the reaction may be concluded as one skilled in the art finds desirable. V

A strong alkaline catalyst is used to efiect the present method. Typical in this respect are alkali metals such as lithium, sodium, and potassium; alkali metal oxides such as lithium oxide, sodium oxide, and potassium oxide; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal lower alkoxides such as lithium butoxide, sodium methoxide, and potassium ethoxide; alkali metal hydrides such as sodium hydride and potassium hydride; alkali metal product is a liquid it may be distilled, if desired.

amides such as sodium amide, lithium amide, and potassium amide; alkali metal lower alkyls and alkenyls such as methyl lithium, ethyl sodium, butyl potassium, allyl sodium, and butenyl potassium; phenylalliyl alkali metals such as benzyl sodium, phenylisopropyl potassium, and alkali metal aromatics such as phenyl sodium, phenyl lithium and phenyl potassium, phenylbutyl sodium; Allin catalysts, which are commercial mixtures of alkali metal alkenyls and alkali metal alkenoxides, such as allyl sodium with sodium allyloxide and butenyl potassium with sodium butenyloxide;. and quaternary ammonium bases such as trimethylbenzylammonium'hydroxide and dimethyldibenzylammonium hydroxide and the corresponding alkoxides such as trimethylbenzylammonium butoxide, choline methoxide, and the like.

Yields up to and over are consistently obtained. In some instances if appreciable amounts of impurities are present in the reactants the yields are somewhat reduced. Accordingly, it is preferred to employ reactants of as high a degree of purity as is conveniently and economically feasible.

a At the conclusion of the reaction there may be added to the reaction system enough anhydrous mineral acid such as sulfuric, phosphoric, or the like, to neutralize the catalyst. The salt formed may be removed such as by filtration. Otherwise, the reaction system may be washed with water and the aqueous layer separated or decanted when the product is a solid. Any solvent employed may be stripped oil, preferably under reduced pressure. Unused reactants when present may be washed out with water or stripped off under reduced pressure. If the Solid roducts may be recrystallized in a conventional manner from a suitable solvent such as hexane, heptane, benzene, toluene, ethylene dichloride, chloroform, or the like.

While the products of this invention may be quite satisfactorily prepared according to the foregoing discussion, it may be advantageousin some instances, where ester groups are concerned'and thedesired R -group is not lower alkyl, to first prepare the lower alkyl ester product and then make the desired highermolecular weight ester product by transesterification. This modification may be used, if desired, to transesterify a single ester group or two ester groups, depending of course on the particular product contemplated.

Transesterification may be conducted preferably in the presence of a strongly acidic esterifying catalyst including sulfuric acid, a lower alkanesulfonic acid, such as butanesulfonic acid, and'an arylsulfonic acid, such as p-toluenesulfonic acid, It is, also, possible to employ a strongly acidic ion-exchange resin, such as a sulfonated polystyrene or sulfonated phenolformaldehyde resin.

Transesterification is preferably conducted at the reflux temperature of the reaction mixture, which is usually in the range of about to 275 0, preferably in the range of about to 225 C. The pressure is adjusted, when necessary, to conform to the above temperatures. Also, if desired, small amounts of an inert volatile organic solvent, such as toluene, xylene, or the like, may be used to help regulate the reflux temperature. A lower alkanol is distilled oil as the transesterification progresses and the reaction is continued until the theoretical amount is collected.

At the termination of the transesterIficat-ion, the product is isolated such as by neutralizing the catalyst, filtering, and distilling, preferably under reduced pressure.

The products of this invention have a wide variety of valuable utilities. The lower molecular weight members are excellent solvents for polymers particularly those in which acrylonitrile or a vinyl ester is the major component. The liquid members are useful as synthetic lubri cents in which instances they consistently exhibit high viscosity indexes, low pour points, and low volatilities. The present products are useful as plasticizers, particularly for polyvinyl chloride; For instance, a mixture of 30 parts of 1,3-bis(Z-methoxycarbonylethyl)-2-imidazolidinone, 45 parts of polyvinyl chloride, 0.75 part of tribasic lead sulfate, and 0.4 part of stearic acid milled for seven minutes at 325 F. gave a tough, flexible film of good quality. Comparable results are obtained with the the other products of this invention. The present products are effective fungicides when applied against Stemphylium sarcinaeforme and especially Monilz'nia fructz'cola in concentrations up to 1.0% in an inert carrier. These products are at the same time non-phytotoxic in concentrations approaching 1% as determined on tomato plants in a standard test.

The method and compounds of this invention may be more fully understood from the following examples which are ofiered by way of illustration but not by way of limitation. ?arts by weight are used throughout.

Example 1 There are added to a reaction vessel, equipped with a stirrer, a thermometer, and a condenser, 236 parts of ethyleneurea and three parts of sodium methoxide. A mixture of 622 parts of methyl acrylate and 1.5 parts of hydroquinone is added over a period of 1.25 hours. The temperature of the mixture rises from 30 to 115 C. during the first 25 minutes and is maintained at 85 to 115 C. by intermittent cooling of the reaction vessel. Two-part portions of sodium methoxide are added at approximately minute intervals until a total of eight additional parts is introduced. The reaction is continued for one-half hour and then thirteen parts of anhydrous phosphoric acid is added. The reaction mixture is stripped at reduced pressure and the product is isolated by distillation at 185 to 230 C. at 1 mm. absolute pressure. The product has an n value of 1.4801, contains 10.50% nitrogen (10.85% theoretical), and corresponds to the name 1,3-bis(Z-methoxycarbonylethyl)-2-in1idazolidinone and the formula CHr-N-CHzCHzCOOCH;

C=O onr-n onronzoooon In a similar manner, there are prepared 1-cyclohexyl-3- (Z-cyanoethyl)-2+imidazolidinone from l-cyclohexyl-Z- imidazolidinone and acrylonitrile, l-(p-octylphenyl) -3-(2- carbamoylethyl) 2 imidazolidinone from l-(p-octylphenyl)-2-imidazolidinone and acrylamide, and 1-(4- methoxyoctyl)-3-[2,5 b-is(methoxycarbonyl)-hexyl]-2- imidazolidinone from 1 (4-methoxyoctyl)-2-imidazolidinone and dimethyl a-rnethylene-a-methyladipate.

Example 2 There are added to a reaction vessel 22 parts of ethyl eneurea and one part of sodium methoxide. There is added 50 parts of ethyl acrylate over a period of six minutes while the reaction mixture is heated to 100 C. Over a period of five hours there are added five portions of sodium methoxide of .25 part each along with ten parts of ethyl acrylate. The temperature of the reaction mixture is slowly increased to 150 C. as the last of the catalyst is added. The temperature is held at 150 C. for an additional hour. The catalyst is neutralized with three parts of phosphoric acid. The product is isolated by distillation at 185 to 205 C. at 0.5 to 0.75 mm. absolute pressure. The product has an 21 value of 1.4741, contains 9.6% nitrogen (9.79% theoretical), and corresponds to the name 1,3-bis(2-ethoxycarbonylethyl)- Z-imidazolidinone and the formula In an analogous way using potassium amide as the catalyst, there are made 1-0ctyl-3-(2-decoxycarbonylethyl)-5,S-dimethyl-Z-imidazolidinone from 1-octyl-5,5-di methy1-2- imidazolidinone and decyl acrylate, 1-(2-hyof sodium methoxide.

10 droxyhexyl) 3 (Z-carbamoylethyl)-4,4,5trimethyl-2- imidazolidinone from 1-(2-hydroxyhexyl)-4,4,5-trimethyl- Example 3 Into a reaction vessel there are added 22 parts of ethyleneurea and 0.25 part of sodium methoxide. Over a ten minute period there is added 64 parts of butyl acrylate. The temperature rises to 50 C. from the exothermic heat of reaction. Twenty minutes after the butyl acrylate is added there is introduced 0.25 part of sodium methoxide and then 0.25 additional part of sodium methoxide after twenty moreminutes. The temperature of the reaction mixture is maintained at C. for two and a half hours. The catalyst is neutralized with phosphoric acid and the product is isolated by distillation at 202 to 204 C. at 0.4 mm. absolute pressure. The product has an n value of 1.4711, contains 8.4% nitrogen (8.2% theoretical), and is named 1,3-bis(2- butoxycarbonylethyl) -2-irnidazolidinone.

In like manner employing lithium oxide as catalyst, there are prepared 1-[4-(6-octenoxy)butyl]-3-(2-carbamoylpropyl)-2-imidazolidinone from 1- [4-(6-octenoxy) butylJ-Z-imidazolidinone and methacrylamide, 1-(8- aminooctyl) 3 (2,5 dibenzyloxycarbonylhexyl) 2- imidazolidinthione from 1-(8-aminooctyl)-2-imidazolidinthione and dibenzyl a-methylene-a-rnethyladipate, and 1- cyano-3- (Z-cyanoethyl)-4,4-diethyl-Z-imidazolidinthione from 1-cyano-4,4-diethyl-Z-imidazolidinthione and acrylonitrile.

Example 4 There are introduced into a reaction vessel 22 parts of ethylen-eurea and 0.25 part of sodium ethoxide. The mixture is heated to 63 C. and 50 parts of methyl methacrylate is added over a period of six minutes causing the temperature to rise above 100 C. There is added after a thirty minute interval 0.25 part of sodium ethoxide and the temperature rises to 136 C. When the heat of reaction subsides the reaction mixture is heated at to C. for three quarters of an hour. Phosphoric acid is added to neutralize the catalyst and the product is isolated by distillation at to 218 C. at 0.3 to 0.75 mm. absolute pressure. The product has an 11 value of 1.4770, contains 9.9% nitrogen (9.8% theoretical), and is identified as 1,3bis(Z-methoxycarbonylpropyl)-2-imidazolidinone.

In an malogous Way using dimethyldibenzy-lammonium hydroxide as catalyst, there are made 1-methyl-3-[2- dimethylcarbamoylethyl]-5-octadecyl Z-imidazolidinone from 1-'nethyl-5octadecyl-2-irnidazolidinone and N,N- dimethylacrylamide, 1-(2-vinoxydecyl)3- (Z-dodecoxycar- -bony1propyl) S-dodecyl-Z-imidazolidinone from 1-(2- vinoxydecyl) 5- dodecyl-Z- imidazolidinone and dodecyl methacrylate and 1-(4-cyanobuty1)-3- (2,5- dibutoxybutoxycarbonylhexyl)-4-penty1-2-imidazolidinthione from 1- (4-cyanobutyl- 3-pentyl- Z-imidazolidinthione and di butoxybutyl a-methylene-oU-methyladipate.

Example 5 There are added to a reaction vessel 86 parts of ethyleneurea and three parts of sodium methoxide. There is added 120 parts of dimethyl a-methylene-a-methyladipate over a period of ten minutes. The reaction mixture is heated to 70 C. and 1.5 parts of sodium methoxide is introduced. There is added rapidly dropwise 280 parts of dimethyl a-met-hylene-M-methyladipate and then one part The reaction mixture is heated at 90 to 110 C. for two hours. There are then added 300 parts of toluene and 100 parts of an aqueous 20% solution of sodium carbonate. The reaction mixture is stirred rapidly and the organic layer is separated, washed with 100 parts of aqueous 10% phosphoric acid, and then washed with 100 parts of water. The organic layer is stripped to 160 C. at 0.1 mm. absolute pressure leaving the product as the residue.

Into a reaction vessel there are added three parts of sodium methoxide and 172 parts of ethyleneurea in 180 parts of toluene- Acrylom'trile, in the amount of 222 6 parts, is added dropwise overa period of one hour at such a rate that the temperature of the reaction mixture, maintained by the heat of reaction, is kept at 100 to 109 C. The toluene layer is removed and 2.6 parts of anhydrous phosphoric acid is added to neutralize the catalyst; The reaction mixture is stripped and the product is isolated by'distillation' at 210 to 214 C. at 0.5 mm. absolute pressure. The product contains 29.05% nitrogen (29.- 15% theoretical) and has an 11 value of 1.4990. The product is identified as 1,3-bis(2-cyanoethyl)-2-imida1- olidinone.

In like manner there are made 1-(3,3,5,5-tetramethyl-2- octenyl) -3-(5-dirnethylcarbamoyI-Z-cyanohexyl) -4-buty1- Z-imidazolidinone from 1-(3,3,5,5-tetramethyl-2-octenyl)- 4-butyl- Z-imidazolidinone and N,N-dimethyl- Z-rnethyl-S- cyano- S-hexenamide, 1-(3-aminopropyl- 3 [2-benzyloxycarbonyl-S-propylcarbamoylhexyl] 4,4-dipropyl- Z-imidazolidinthione from 1-(3-aminopropyl)-4,4-dipropyl-2-imidazolidinthione and benzyl Z-methylene-S-propylcarbamoylhexanoate, and 1cycloheXyl-3-(Z-cyclohexoxycarbonyl-5-cyanohexyl) -5,S-dimethyl-Z-imidazolidinone from 1- cyclohexyl-S,S-dimethyl-Z-imidazolidinone and cyclohexyl 2-methylene-5-cyanohexanoate. V

Example 7 There are mixed in a reaction vessel 202 parts of l-(2- 'vinoxyethyl)-2-imidazolidinone and onepart of sodium methoxide. There is then added 74 parts of acrylonitrile in dropwise manner over. a period of 22 minutes. The heat of reaction induces a rise in temperature to 70 C. After the heat of reaction subsides there is added 0.5 part of sodium methoxide. After a total time of two hours has elapsed the catalyst is neutralized with sulfuric acid. The product is isolated by distillation at 166 to 168 C. at 0.3 mm. absolute pressure. The product contains 119.9% nitrogen (20.08% theoretical), has an 71 value of 1.4970, and is identified as 1-(2-vinoxyethyD-3- (Z-cyanoethyl)-2-imidazolidinone. This compound may be homopolymerized with Friedel-Crafts catalysts. It may be copolymerized with acrylate esters, maelic anhydride, alkyl furnarates, and other vinyl compounds in the presence of free-radical initiators.

In a similar manner, using sodium as a catalyst, there are prepared 1-v1'nyl-3 -(2-cyanoethyl) -2-imidazolidinone' from 1- vinyl- 2'imidazolidinone and acrylonitrile, l-(p-.

octylphenyl-3-(2,5 dioctoxycarbonylhexyl)-2-imidazolidinthione from l-(P-Octylphenyl) -2-imidazolidinthione and dioctyl wmethylene-d-methyladipate, 1-(2-benzyloxycarb onylethyl) -3 ,3 -dimethyl-4- (p-dodecylphenyl 2-piper azinone from 3,3-dimethyl-4-(p-dodecylphenyl)- 2-piperazinone and benzyl acrylate, and l-(2-carbarnoylpropyl) 3,3-dimethyl-4- (3-cyanopropyl) -2-piperazinthione from methacrylamide and 3,3-dimethyl-4 (3-cyanopropyl) -2- piperazinthione.

Example 8 There are added to a reaction vessel 65 parts of l-(2- hydroxyethyl)-2-imidazolidinone, 150 parts of methyl methacrylate and four parts of di-fi-naphthol. A solution of 4.5 parts of sodium methoxide in 30 parts of methanol is added slowly while the reaction mixture is heated to reflux and the distillate is removed at a high reflux rate. The head temperature is held at a temperature no higher than 95 C. and the pot temperature is held below 135 C. The reaction is concluded after one hour. The distillate is methanol in amounts equal to the theoretical amount for transesterification. The reaction mixture is shaken with sulfuric acid and then distilled. The product distills at 170 C. at 0.1. mm. absolute pressure. The product contains 56.1% carbon (56.4% theoretical), 10.2% nitrogen (9.4% theoretical), and 7.5% hydrogen (7.4% theoretical). The product is identified as 1-(2- methacryloyloxyethyl) 3 (Z-methoxycarbonylpropyl)- Z-imidazolidinone and corresponds to the formula CHz-OH: cnz=coooon onn r N-CHCOOOHs on, o dug This material gives a hard homopolymer when heated with free-radical generating catalysts. It copolymerizes well with acrylates, acrylonitrile, and other vinyl monomers to give polymers useful as coatings, adhesives, and fibers.

Similarly, there are prepared l-(6-acryloyloxyhexyl)-3- (Z-ethoxycarbonylethyl) 2 piperazinone from l-(6-hydroxyhexyl) 2 piperazinone and ethyl acrylate, l-(8- acryloyloxyoctyl) 3 (2-butoxycarbonylethyl)-2-piperirnidinone from l-(8-hydroxyoctyl)-2-piperimidinone and butyl acrylate, and 1-(4-rnethacryloyloxybutyl) 3 (2- butoxycarbonylpropyl) 2 piperazinthione from l-(4-hydroxybutyl)-2-piperazinthione and butyl methacrylate.

Example 9 To a mixture of 0.5 part of sodium methoxide and 27 parts of 3,3,4,5-tetran1ethyl 2 piperazinone there is added dropwise 15.5 parts of methyl acrylate. An appreciable heat of reaction is noticed causing the temperature to rise to 65 C. After the heat of reaction abates there is added 0.4 part of sodium methoxide. The reaction mixture is held at 96 C. forthree hours after which time 0.8 part of phosphoric acid is added. The product is isolated by distillation. Nitrogen analysis corresponds to l-(Z-methoxycarbonylethyl) 3,3,4,5 tetrarnethyl-Z- piperazinone. The product corresponds to the formula Example 10 There are added to a reaction flask 29,parts of ethylenethiourea and two parts of sodium methoxide. A mixture of 100 parts of methyl methaerylate and two parts of 13 sodium methoxide is added in a fifteen minute period. The reaction mixture is heated to 120 C. and maintained at that level for two hours. The catalyst is neutralized with sulfuric acid and the product is isolated by distillation at 187 to 222 C. at 0.9 mm. absolute pressure. The product contains 9.0 nitrogen (9.26% theoretical) and corresponds to 1,3-bis(Z-methoxycarbonylpropyl)-2-imidazolidinthione with the formula 5 CHz-wN-CHgOHCOOOH;

o=s HrN CHzCllllc O O CH;

There are prepared in like manner, 1-phenyl-3-(2-cyanoethyl)-4-dodecyl-2-piperimidinone from 1-phenyl-4-do decyl- 2 piperimidinone and acrylonitrile, 1,3-bis(2-carbamoylethyl) 6,6 dibutyl-Z-piperimidinone from l-(2- carbamoylethyl) 6,6 dibutyl-Z-piperimidinone and acrylamide, and 1-(2-vinoxyethyl) 3 (2-methoxyoctoxycarbonylethyl) 4,5,6 trimethyl 2 piperimidinthione from l-(2-vinoxyethyl) 4,5,6 trimethyl-2-piperimidinthione and methoxyoctyl acrylate.

Example 11 There are added to a reaction vessel 21 parts of 1- (3-aminopropyl) -2-piperin1idinone, 62 parts of methyl acrylate, and three parts of potassium ethoxide. A heat of reaction is observed and the reaction mixture is heated to 140 to 145 C. for one and one-quarter hours. The catalyst is neutralized with sulfuric acid and the product is isolated by distillation. Elemental analysis indicates that the product is 1-(3-aminopropy1)-3-(2-methoXycarbonylethyl)-2-piperimidinone, having the formula CH: C CH1 In like manner there are made 1-(8-methoxyoctyD-3- [Z-methylcarbamoylethyl] 5,5 dipropyl 2 pipen'midione from 1 (S-methoxyoctyl) 5,5 dipropyl-2-piperimidinone and N-methylacrylamide, 1-benzyl-4-(2,5-di butoxycarbonylhexyl) 5 octyl-6-hexyl-2-piperidinthione from l-benzyl 5 octyl-d-hexyl-Z-piperidinthione and dibutyl a-methylene-a'-methyladipate, and 1-(2-butenyl)-3- (Z-methoxycarbonyl 5 benzoxycarbonylhexyl)-4,5-diethyl 2 piperimidinone from 1-(2-butenyl)-4,5-diethyl- 2-piperimidione and methyl benzyl a-methylene-a'-methyladipate.

Example 12 A reaction vessel is charged with 150 parts of 1,3- bis(Z-methoxycarbonylethyl)-2-irnidazolidinone and 337 parts of Z-ethylhexanol. The solution is heated at reflux until water no longer collects in the Dean-Stark water separator attached to the flask. There is added five parts of sulfuric acid and the Water separator is replaced by a column and distilling head. The reaction mixture is held at 150 C. Methanol is removed until the theoretical amount is collected. The reaction mixture is cooled, washed with two 50-part portions of aqueous sodium carbonate and 150 parts of water and then dried over anhydrous magnesium sulfate. Two parts of phosphoric acid is added and the mixture is distilled. The product distills at 250 to 270 at 0.4 mm. absolute pressure, contains 6.1% nitrogen (6.16% theoretical), and is identified as 1,3-bis(2,2'-ethylhexoxycarbonylethyl)- Z-imidazolinone.

In a similar Way, l,3-bis(2,2'-e ylhexoxycarbonylethyD-Z-piperlmidinone and 1,4-bis(2,2-ethylhexoxycarbonylethyD-Z-piperazinone are prepared from the corresponding methyl esters.

1 4 Example 13 There is transesterified, according to the method of Example 12, the compound 1,3-bis(Z-methoxycarbonylethyl)-2-imidazolidiuone (202 parts) with a mixture of octanol, nonanol, and decanol (450 parts) to form a compound that distills at 255 to 270 C. at 0.25 mm. absolute pressure, contains 6.0% nitrogen (5.8% theoretical), and corresponds to the compound 1,3-bis(2-(C C C alkoxyc arb onylethyl) -2-irnid azolidinone.

Example 14 There is transesterified 1,3-bis(2-methoxycarbonylethyl)-2-irr-.idazolidinone (200 parts) with dodecanol (453 parts) in the presence of sulfuric (14 parts) acid according to Example 12. The product distills at 2 0 to 290 C. at 0.35 mm. absolute pressure, has an n value of 1.4648, contains 5.0% nitrogen (4.7% theoretical), and

is identified as 1,3-bis(Z-dodecoxycarbonylethyl)-2-imidazolidinone.

Similarly, there are made by transesterification 1,3- bis(Z-dodecoxycarbonylethyl)-2-piperimidinthione and 1, 4-bis(2-dodecoxycarbonylethyl)-2-piperazintlnone from the corresponding methyl esters.

Example 15 There are charged to a reaction vessel 198 parts of butanol, 175 parts of 1,3-bis(2,5-dirnethoxycarbonylhexyl)-2-imidazolidinone, and one part of sulfuric acid. The mixture is heated at reflux and the methanol removed as it separated. After the theoretical amount of methanol is collected the reaction mixture is cooled and washed with parts of aqueous 10% sodium bicarbonate and 100 parts of water. The mixture is stripped and the product is distilled at reduced pressure. The product contains 4.19% nitrogen (4.20% theoretical) and is identified as 1,3-bis(2,5-dibutoxycarbonylhexyl) -2 imidazolidinone.

Using the same method there are made 1,3-bis(2,5-dibutoxycarbonylhexyl)-2-piperimidinone and 1,4-bis(2,5- dibutoxycarbonylhexyl)-2-piperazinone from the corresponding methyl esters.

Example 16 Using the method of Example 15 there is transesterified 1,3-bis(2,5-dimethoxycarbonylhexyl)-2 imidazolidinone with Z-ethylhexanol to yield 1,3-bis[2,5-di(2-ethylhexoxycarbonyDhexyll-2-imidazolidinone. The product contains 3.10% nitrogen (3.19% theoretical).

Similarly, there are produced 1,3'bis [2,5-di(2-ethylhexoxycarbonyhhexyl]-2-piperimidinone and 1,4-bis[2,5- di(Z-ethylhexoxycarbony-l)hexyl]2-piperazinone from the corresponding methyl esters.

1 claim:

1. An adduct of the compounds /NH 0 H Y and CH2=C|J '1 CHzOHzCH(CHa)T having the formula /NCH1CHT (I'll H2CH3CH(CH3)T Y in which L is a divalent chain of two to three carbon atoms and one nitrogen atom wherein said nitrogen atom is at least two carbon atoms removed from the other nitrogen atom in the heterocyclic amide when that amide is considered in a counterclockwise direction, the remain- 1 5 ing available carbon valences in said L chain being satisfied by members from the group consis ing of a hydrogen atom and alkyl groups whose total carbon content is no greater than eighteen, the available valence of said nitrogen atom in said L chain being satisfied by a member from the group consisting of the group, alkyl, cycloalkyl and alkylcycloalkyl groups of one to eighteen carbon atoms, aryl, alkylaryl, arylalkyl and alkylarylalkyl groups of six to eighteen carbon atoms,

hydroxyalkyl groups of two to eight carbon atoms in which the hydroxy group is no closer than the beta position with respect to said nitrogen atom in'said L chain, alkenyl groups of two to eighteen carbon atoms, aminoalkyl groups of two to eight carbon atoms in which the amino group is no closer than the beta position with respect to said nitrogen atom in said L chain, allcoxyalkyl groups containing up to nineteen carbon atoms in which the alkoxy portion contains up to eight carbon atoms and the alkyl portion contains at least two carbon atoms,

. alkenoxyalkyl groups containing up to nineteen carbon atoms in which the alkenoxy portion contains up to eight carbon atoms and the alkyl portion contains at least two carbon atoms, cyano groups, and cyanoalkyl groups in which the alkyl group contains up to eight carbon atoms, Y is a chalcogen having an atomic weight of 16 to 32, and T is a member from thegroup consisting of a cyano group, the group --CONZ in which Z is a member from the group consisting of a hydrogen atom and alkyl groups or" one to eight carbon atoms, and the group --COOR in which R is a member from the group consisting of alkyl groups of one to fourteen carbon atoms, alkoxyalkyl groups of two to fourteen carbon atoms, aralkyl and alkaralkyl groups of seven to fourteen carbon atoms, and cycloalkyl and alkylcycloalkyl groups of three to fourteen carbon atoms.

2. An adduct of the compounds NH C H Y and ' CHFOC 0 0R CH2CH2CH(CH:\) COOR having the formula /NCH2CEC 0 OR g!) CHnCH2CH(CHs)COOR in which L is a divalent chain of two to three carbon atoms and one nitrogen atom wherein said nitrogen atom lti V is at least. two carbon atoms removed from the other nitrogen atom in the heterocyclic amide when that amide is considered in a counterclockwise direction, the remainng available carbon valences in said L chain being satisfied by hydrogen atoms, the remaining available nitrogen valences in said L chain being satisfied by an alkyl group of 1 to 18 carbon atoms, Y is a chalcogen having an atomic weight of 16 to 32 and R is an alkyl group of one to fourteen carbon atoms.

3. An adduct of the compounds and having the formula NOHZ? HO O 0 R 7 (n7 CH2CHQCH(CH3)COOR in which L is a divalent chain of two to three carbon atoms and one nitrogen atom wherein said nitrogen atom is at least two carbon atoms removed from the other nitrogen atom in the heterocyclic amide when that amide is considered in a counterclockwise direction, the remaining availablecarbon valences in said L chain being satisfled by alkyl groups whose total carbon content is no greater than 18, the remaining available nitrogen valences in said L chain being satisfied by an alkyl group of 1 to 18 carbon atoms, Y is a chalcogen having an atomic weight of 16 to 32 and R is an alkyl group of one to fourteen carbon atoms.

4. An adduct of ethyleneurea and a dialkyl tZ-m$thy1- ene-d-methyladipate having the formula in which the alkyl portion contains one to fourteen carbon atoms.

5. 1,3 bis(2,5 dimethoxycarbonylhexyl) 2 imidazolidinone.

References Cited in the file of this patent FOREIGN PATENTS 859,314 Germany Dec. 18, 1952 722,541 Great Britain Jan. 26, 1955 306,990

Switzerland July 16, 1955 

1. AN ADDUCT OF THE COMPOUNDS 